Olefins are polymerized by a catalyst system that includes a nickel[II] complexes of selected monoanionic bidentate ligands. Some of these complexes are also novel.
Polymers of ethylene and-other olefins are important items of commerce, and these polymers are used in a myriad of ways, from low molecular weight polyolefins being used as a lubricant and in waxes, to higher molecular weight grades being used for fiber, films, molding resins, elastomers, etc. In most cases, olefins are polymerized using a catalyst, often a transition metal compound or complex. These catalysts vary in cost per unit weight of polymer produced, the structure of the polymer produced, the possible need to remove the catalyst from the polyolefin, the toxicity of the catalyst, etc. Due to the commercial importance of polymerizing olefins, new polymerization catalysts are constantly being sought.
This invention concerns a process for the polymerization of an olefin selected from one or more of R67CHxe2x95x90CH2, cyclopentene, a styrene, a norbornene or H2Cxe2x95x90CH(CH2)sCO2R77, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C., R67CHxe2x95x90CH2, cyclopentene, a styrene, a norbornene, or H2Cxe2x95x90CH(CH2)sCO2R77, optionally a Lewis acid, and a compound of the formula: 
wherein:
Ar1, Ar2, Ar4, Ar5, Ar10, Ar11, Ar12 and Ar13 are each independently aryl or substituted aryl;
R1 and R2 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R1 and R2 taken together form a ring, and R3 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R1, R2 and R3 taken together form a ring;
A is a xcfx80-allyl or xcfx80-benzyl group;
R10 and R15 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
R11, R12, R13, R14, R16, R17, R18, R19, R20, R21, R30, R31, R32, R33, R34, R35, R50, R51, R52, R53 and R54 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group, and provided that any two of these groups vicinal to one another taken together may form a ring;
K is N or CR27;
R22 is hydrocarbyl, substituted hydrocarbyl, xe2x80x94SR117, xe2x80x94OR117, or xe2x80x94NR1182, R24 is hydrogen, a functional group, hydrocarbyl or substituted hydrocarbyl, and R27 is hydrocarbyl or substituted hydrocarbyl, and provided that R22 and R or R24 and R27 taken together may form a ring;
R117 is hydrocarbyl or substituted hydrocarbyl;
each R118 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
G and L are both N or G is CR57 and L is CR55;
R55, R56 and R57 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or any two of R55, R56 and R57 taken together form a ring;
R67 is hydrogen, alkyl or substituted alkyl;
R77 is hydrocarbyl or substituted hydrocarbyl;
R78 is hydrocarbyl or substituted hydrocarbyl;
R79, R80, R81, R82, R83, R84, R85, R86, R87, R88 and R89 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
R90, R91, R92 and R93 are each independently hydrocarbyl or substituted hydrocarbyl;
R94 and R95 are each independently hydrocarbyl or substituted hydrocarbyl;
R96, R97, R98, and R99 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
both of T are S (sulfur) or NH (amino);
each E is N (nitrogen) or CR108 wherein R108 is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
R100, R101, R102, R103, R104, R105, R106, and R107 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
R109, R110, R111, R112, R113, R114, R115 and R116 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
s is an integer of 1 or more; and
R28 and R29 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
and provided that when H2Cxe2x95x90CH(CH2)sCO2R77 is present, R67 CHxe2x95x90CH2 is also present.
This invention also concerns a process for the polymerization of an olefin selected from one or more of R67 CHxe2x95x90CH2, a styrene, a norbornene or H2Cxe2x95x90CH(CH2)sCO2R77, comprising, contacting, at a temperature of about xe2x88x92100xc2x0 C. to about +200xc2x0 C., R67CHxe2x95x90CH2, cyclopentene, a styrene, a norbornene, or H2Cxe2x95x90CH(CH2)sCO2R77, optionally a Lewis acid, and a compound of the formula: 
wherein:
L1 is a neutral monodentate ligand which may be displaced by said olefin, and L2 is a monoanionic monodentate ligand, or L1 and L2 taken together are a monoanionic bidentate ligand, provided that said monoanionic monodentate ligand or said monoanionic bidentate ligand may add to said olefin;
Ar1, Ar2, Ar4, Ar5, Ar10, Ar11, Ar12 and Ar13 are each independently aryl or substituted aryl;
R1 and R2 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R1 and R2 taken together form a ring, and R3 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R1, R2 and R3 taken together form a ring;
R10 and R15 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
R11, R12, R13, R14, R16, R17, R18, R19, R20, R21, R30, R31, R32, R33, R34, R35, R50, R51, R52, R53 and R54 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group, and provided that any two of these groups vicinal to one another taken together may form a ring;
K is N or CR27;
R22 is hydrocarbyl, substituted hydrocarbyl, xe2x80x94SR117, xe2x80x94OR117, or xe2x80x94NR1182, R24 is hydrogen, a functional group, hydrocarbyl or substituted hydrocarbyl, and R27 is hydrocarbyl or substituted hydrocarbyl, and provided that R22 and R24 or R24 and R27 taken together may form a ring;
R117 is hydrocarbyl or substituted hydrocarbyl;
each R118 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
G and L are both N or G is CR57 and L is CR55;
R55, R56 and R57 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or any two of R55, R56 and R57 taken together form a ring;
R67 is hydrogen, alkyl or substituted alkyl;
R77 is hydrocarbyl or substituted hydrocarbyl;
R78 is hydrocarbyl or substituted hydrocarbyl;
R79, R80, R81, R82, R83, R84, R85, R86, R87, R88 and R89 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
R90, R91, R92 and R93 are each independently hydrocarbyl or substituted hydrocarbyl;
R94 and R95 are each independently hydrocarbyl or substituted hydrocarbyl;
R96, R97, R98, and R99 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
both of T are S (sulfur) or NH (amino);
each E is N (nitrogen) or CR108 wherein R108 is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
R100, R101, R102, R103, R104, R105, R106, and R107 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
R109, R110, R111, R112, R113, R114, R115 and R116 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
s is an integer of 1 or more; and
R28 and R29 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
and provided that when H2Cxe2x95x90CH(CH2)s CO2R77 is present, R67CHxe2x95x90CH2 is also present.
Also described herein is a compound of the formula: 
wherein:
L1 is a neutral monodentate ligand which may be displaced by said olefin, and L2 is a monoanionic monodentate ligand, or L1 and L2 taken together are a monoanionic bidentate ligand, provided that said monoanionic monodentate ligand or said monoanionic bidentate ligand may add to said olefin;
Ar1, Ar2, Ar4, Ar5, Ar10, Ar11, Ar12 and Ar13 are each independently aryl or substituted aryl;
R1 and R2 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R1 and R2 taken together form a ring, and R3 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R1, R2 and R3 taken together form a ring;
R10 and R15 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
R11, R12, R13, R14, R16, R17, R18, R19, R20, R21, R30, R31, R32, R33, R34, R35, R50, R51, R52, R53 and R54 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group, and provided that any two of these groups vicinal to one another taken together may form a ring;
K is N or CR27;
R22 is hydrocarbyl, substituted hydrocarbyl, xe2x80x94SR117, xe2x80x94OR117, or xe2x80x94NR1182, R24is hydrogen, a functional group, hydrocarbyl or substituted hydrocarbyl, and R27 is hydrocarbyl or substituted hydrocarbyl, and provided that R22 and R24 or R24 and R27 taken together may form a ring;
R117 is hydrocarbyl or substituted hydrocarbyl;
each R118 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
G and L are both N or G is CR57 and L is CR55;
R55, R56 and R57 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or any two of R55, R56 and R57 taken together form a ring;
R78 is hydrocarbyl or substituted hydrocarbyl;
R79, R80, R81, R82, R83, R84, R85, R86, R87, R88 and R89 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
R90, R91, R92 and R93 are each independently hydrocarbyl or substituted hydrocarbyl;
R94 and R95 are each independently hydrocarbyl or substituted hydrocarbyl;
R96, R97, R98, and R99 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
both of T are S (sulfur) or NH (amino);
each E is N (nitrogen) or CR108 wherein R108 is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
R100, R101, R102, R103, R104, R105, R106, and R107 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
R109, R110, R111, R112, R113, R114, R115 and R116 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group; and
R28 and R29 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl.
Also disclosed herein is a compound of the formula 
wherein:
R58, R59, R60, R62, R63 and R64 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group, and provided that any two of these groups vicinal to one another taken together may form a ring, or if vicinal to R61 or R65 form a ring with them;
R66 is hydrogen, hydrocarbyl or substituted hydrocarbyl; and
R61 and R65 are each independently hydrocarbyl containing 2 or more carbon atoms, or substituted hydrocarbyl containing 2 or more carbon atoms, and provided that R61 and R65 may form a ring with any group vicinal to it.
This invention also concerns a compound of the formula 
wherein:
R68 is hydrocarbyl, substituted hydrocarbyl, xe2x80x94SR117, xe2x80x94OR117, or xe2x80x94NR1182, R76 is hydrogen, a functional group, hydrocarbyl or substituted hydrocarbyl, and R75 is hydrocarbyl or substituted hydrocarbyl, and provided that R68 and R76 or R75 and R76 taken together may form a ring;
R117 is hydrocarbyl or substituted hydrocarbyl;
each R118 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
R70, R71 and R72 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
R69 and R73 are hydrocarbyl containing 3 or more carbon atoms, substituted hydrocarbyl containing 3 or more carbon atoms or a functional group;
and provided that any two of R70, R71, R72, R69 and R73 vicinal to one another together may form a ring.
Herein, certain terms are used. Some of them are:
A xe2x80x9chydrocarbyl groupxe2x80x9d is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is preferred that hydrocarbyl groups herein preferably contain 1 to about 30 carbon atoms.
By xe2x80x9csubstituted hydrocarbylxe2x80x9d herein is meant a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain preferably 1 to about 30 carbon atoms. Included in the meaning of xe2x80x9csubstitutedxe2x80x9d are heteroaromatic rings.
By xe2x80x9c(inert) functional groupxe2x80x9d herein is meant a group other than hydrocarbyl or substituted hydrocarbyl which is inert under the process conditions to which the compound containing the group is subjected. The functional groups also do not substantially interfere with any process described herein that the compound in which they are present may take part in. Examples of functional groups include halo (fluoro, chloro, bromo and iodo), ether such as xe2x80x94OR25, xe2x80x94CO2R25, xe2x80x94NO2, a xe2x80x94NR252, wherein R25 is hydrocarbyl or substituted hydrocarbyl. In cases in which the functional group may be near a nickel atom the functional group should not coordinate to the metal atom more strongly than the groups in compounds which are shown as coordinating to the metal atom, that is they should not displace the desired coordinating group.
By a xe2x80x9cpolymerization processxe2x80x9d herein (and the polymers made therein) is meant a process which produces a polymer with a degree of polymerization (DP) of about 5 or more, preferably about 10 or more, more preferably about 40 or more [except where otherwise noted, as in P in compound (XVII)]. By xe2x80x9cDPxe2x80x9d is meant the average number of repeat (monomer) units in the polymer.
By xe2x80x9carylxe2x80x9d herein is meant a monovalent radical whose free valence is to a carbon atom of an aromatic ring. Unless otherwise noted herein, preferred aryl groups contain carbocyclic rings, but heterocyclic rings are also included within the definition of xe2x80x9carylxe2x80x9d. The aryl radical may contain one ring or may contain 2 or more fused rings, such as 9-anthracenyl or 1-naphthyl. Unless otherwise stated aryl groups preferably contain 5 to 30 carbon atoms.
By xe2x80x9csubstituted arylxe2x80x9d herein is meant an aryl radical substituted with one or more groups that do not interfere with the synthesis of the compound or the resulting polymerization. Suitable substituents include alkyl, aryl such as phenyl, halo, alkoxy, ester, dialkylamino and nitro. Unless otherwise stated, substituted aryl groups contain 5 to about 30 carbon atoms.
By a xe2x80x9cmonoanionic ligandxe2x80x9d is meant a ligand with one negative charge.
By a xe2x80x9cneutral ligandxe2x80x9d is meant a ligand that is not charged.
xe2x80x9cAlkyl groupxe2x80x9d and xe2x80x9csubstituted alkyl groupxe2x80x9d have their usual meaning (see above for substituted under substituted hydrocarbyl). Unless otherwise stated, alkyl groups and substituted alkyl groups preferably have 1 to about 30 carbon atoms.
By a styrene herein is meant a compound of the formula 
wherein R43, R44, R45, R46 and R47 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, all of which are inert in the polymerization process. It is preferred that all of R43, R44, R45, R46 and R47 are hydrogen. Styrene (itself) is a preferred styrene.
By a norbornene is meant ethylidene norbornene, dicyclopentadiene, or a compound of the formula 
wherein R40 is hydrogen or hydrocarbyl containing 1 to 20 carbon atoms. It is preferred that R40 is hydrogen or alkyl, more preferably hydrogen or n-alkyl, and especially preferably hydrogen. The norbornene may be substituted by one or more hydrocarbyl, substituted hydrocarbyl or functional groups in the R40 or other positions, with the exception of the vinylic hydrogens, which remain. Norbornene (itself), dimethyl endo-norbornene-2,3-dicarboxylate, t-butyl 5-norbornene-2-carobxylate are preferred norbornenes and norbornene (itself) is especially preferred.
By a xcfx80-allyl group is meant a monoanionic ligand with 3 adjacent sp2 carbon atoms bound to a metal center in an xcex73 fashion. The three sp2 carbon atoms may be substituted with other hydrocarbyl groups or functional groups. Typical xcfx80-allyl groups include 
wherein R is hydrocarbyl. By a xcfx80-benzyl group is meant xcfx80-allyl ligand in which two of the sp2 carbon atoms are part of an aromatic ring. Typical xcfx80-benzyl groups include 
xcfx80-Benzyl compounds usually initiate polymerization of the olefins fairly readily even at room temperature, but xcfx80-allyl compounds may not necessarily do so. Initiation of 7E-allyl compounds can be improved by using one or more of the following methods:
Using a higher temperature such as about 80xc2x0 C.
Decreasing the bulk of the monoanionic ligand, such as aryl being 2,6-dimethylphenyl instead of 2,6-diisopropylphenyl.
Making the xcfx80-allyl ligand more bulky, such as using 
rather than the simple xcfx80-allyl group itself.
Having a Lewis acid or a material that acts as a Lewis acid present while using a xcfx80-allyl or xcfx80-benzyl group, especially a functional xcfx80-allyl or xcfx80-benzyl group. Relatively weak Lewis acids such as triphenylborane, tris(pentafluorophenyl)borane, tris(3,5-trifluoromethylphenyl)borane, and poly(methylaluminoxane) are preferred. Suitable functional groups include chloro and ester.
Lewis acids may also be optionally present when compounds containing L1 and/or L2 are present in the polymerization, even when L2 is not a xcfx80-allyl or xcfx80-benzyl group. It is believed that the Lewis acid, if present, may help to remove L1 (if present) from the nickel atom, thereby facilitating the coordination of the olefin to the Ni atom. If a compound containing L1 and/or L2 does not act as a polymerization catalyst, it is suggested that a Lewis acid, such as those mentioned above be added to the process to determine if polymerization will then take place. Such testing requires minimal experimentation, and is illustrated in the Examples. Not surprisingly, with any particular set of polymerization process ingredients, some Lewis acids may be more effective than others.
In preferred olefins herein, R67 is hydrogen or xcex1-alkyl containing 1 to 20 carbon atoms (an xcex1-olefin), more preferably n-alkyl containing 1 to 8 carbon atoms, or more preferably hydrogen (e.g., ethylene) or methyl (e.g., propylene), and especially preferably hydrogen. A combination of ethylene and H2Cxe2x95x90CHR67 wherein R67 n-alkyl containing 1 to 8 carbon atoms is also preferred, and a combination of ethylene and propylene is more preferred. It is also preferred that s is 2 or more, and/or R77 is alkyl, especially preferably methyl or ethyl. When H2Cxe2x95x90CH(CH2)sCO2R77 is present as one of the olefins, it is preferred that R67 is hydrogen.
While not all homopolymers and copolymers of the olefinic monomers useful herein can be made using the polymerization processes described herein, most homopolymers and many copolymers can be made. The following homopolymers can be readily made in these polymerization processes: polyethylene, polystyrene, a polynorbornene, poly-xcex1-olefins (often lower molecular weight polymers obtained), polycyclopentene (often lower molecular weight polymers obtained). Attempted homopolymerization of functionalized norbornenes often does not proceed, nor do homopolymerizations of compounds of the formula H2Cxe2x95x90CH(CH2)sCO2R77. Many copolymers can be made, including ethylene/xcex1-olefins, styrene/norbornene copolymers, copolymers of 2 or more norbornenes including functionalized norbornenes, copolymers of ethylene and cyclopentene, copolymers of ethylene and a norbornene, and copolymers of ethylene and H2Cxe2x95x90CH(CH2)sCO2R77.
Not every variation of every nickel complex listed in the various polymerizations will make every one of the polymers listed immediately above. However, many of them will make most if not all of these types of polymers. While no hard and fast rules can be given, it is believed that for polymerizations which include ethylene and/or xcex1-olefins, steric hindrance about the nickel atom caused by substituent groups is desirable for making polymers, especially higher molecular weight polymers, while for polymers containing one or more of a styrene and/or a norbornene such steric hindrance is not as important.
The Ni[II] complexes that are useful herein for the polymerization of ethylene contain a bidentate monoanionic ligand (other than a combined L1 and L2 ) in which the coordinating atoms are 2 nitrogen atoms, a nitrogen atom and an oxygen atom, a phosphorous atom and a sulfur atom, or an oxygen atom and a sulfur atom. Compounds of formulas (I) through (VI), (XVIII), (XXVII), and (XXXVII)-(XXXX) can be made by reaction of 2 moles of the anionic form of the ligand with one mole of the appropriate nickel allyl or benzyl precursor (XXI), 
wherein X is preferably chlorine or bromine and A is a xcfx80-allyl or xcfx80-benzyl group, to form the nickel compound (see Examples 17-40 and 469-498).
Compounds of formulas (VII) through (XII), (XIX), (XXVIII), and (XXXXI)-(XXXXIV) can be synthesized by protonation of a suitable Ni[0] or Ni[II] precursor by the neutral ligand or by reaction of a suitable Ni[II] precursor with the anionic form of the ligand. Examples of suitable Ni[0] and Ni[II] precursors include Ni(1,4-cyclooctadiene)2, (N,N,Nxe2x80x2Nxe2x80x2-tetramethylethylenediamine)NiMe2, 2,2xe2x80x2-bipyridineNiMe2, (MePPh2)3NiMe2, [Ni(OMe)Me(PPh3)]2, [Ni(OMe)Me(PMe3)]2, NiBr2, N,N,Nxe2x80x2Nxe2x80x2-tetramethylethylenediamine)Ni (acetylacetonate)2, (1,2-dimethoxyethane)NiBr2, N,N,Nxe2x80x2Nxe2x80x2-tetramethylethylenediamine)Ni(CH2xe2x95x90CHCO2CH3)2, (pyridine)2Ni(CH2xe2x95x90CHCO2CH3)2, and (acetylacetonate)Ni(Et)(PPh3). The addition of phosphine or ligand xe2x80x9cspongesxe2x80x9d such as CuCl, BPh3 or tris(pentafluorophenyl)borane may aid such reactions.
Some of the nickel compounds herein such as (XXXIX), (XXXX), (XXXXIII) and (XXXXIV) may exist as xe2x80x9cdimersxe2x80x9d or monomers, or in equilibrium between the two. The dimer contains two nickel atoms, each nickel atom being coordinated to L1 and L2, wherein L1 and L2 combined may be a bidentate monoanionic ligand such as a xcfx80-allyl or xcfx80-benzyl group, and both Ni atoms xe2x80x9csharexe2x80x9d coordination to each of the other ligands present. As described herein, depiction of the monomeric compound also includes the dimeric compound, and vice versa. Whether any particular nickel compound is (predominantly) a monomer or dimer, or both states are detectable will depend on the ligands present. For instance it is believed that as the ligands become more bulky, especially about the nickel atom, the tendency is to form a monomeric compound.
Ligands for compounds (I) and (VII) of the formula 
can be made by reaction of an alpha-diimine of the formula Ar1Nxe2x95x90CR1xe2x80x94CR2xe2x95x90NAr2 with one equivalent of a compound of the formula R3 Li, see for instance M. G. Gardner, et al., Inorg. Chem., vol. 34 p. 4206-4212 (1995). In another case, a ligand of the formula 
can be made by the condensation of 1,2-cyclohexadione with the corresponding aromatic amine(s), see for instance R. van Asselt, et. al, Recl. Trav. Chim. Pays-Bas, vol. 113, p. 88-98 (1994). Note that in (XXIII) R1, R2 and R3 taken together form a ring, with R2 and R3 both xe2x80x9cpart ofxe2x80x9d a double bond to the same carbon atom. These ligands can then be converted to their corresponding nickel complexes by the methods described above.
Compounds of the formula (II) can be made by the reaction of a ligand of the formula 
while compounds of the formula (VIII) can be made from the protonated form of (XIII). (XIII) can be made from the corresponding salicylaldehyde (when R10 is hydrogen) and aromatic amine, followed by reaction with an alkali metal base (such as an alkali metal hydride) to form the aryloxide.
(III) and (IX) can be made by reacting pyrrole-2-carboxyaldehyde with the appropriate aromatic amine to form the pyrrole-2-imine, followed by reaction with a strong base to form the pyrrole anion, and then reaction with the nickel precursors described above to form the nickel[II] complex.
Similarly, (IV) and (X) can be formed from an alkali metal thiophene-2-carboxylate and the nickel precursors described above.
When K is CR27 the ligand for (V) and (XI) can be made by the reaction of the corresponding ketone (which may contain other functional groups) with an aromatic amine to give 
which is a tautomer of 
Useful ketones for making (V) and (XI) include ethyl acetoacetate, ethyl 2-ethylacetoacetate, isobutyl acetoacetate, t-butyl acetoacetate, S-t-butyl acetoacetate, allyl acetoacetate, ethyl 2-methylacetoacetate, methyl 2-chloroacetoacetate, ethyl 2-chloroacetoacetate, methyl 4-chloroacetoacetate, ethyl 4-chloroacetoacetate, ethyl 4,4,4-trifluoroacetoacetate, S-methyl 4,4,4-trifluoro-3-oxothiobutyrate, 2-methoxyethyl acetoacetate, methyl 4-methoxyacetoacetate, methyl propionylacetate, ethyl propionyl acetate, ethyl isobutyrylacetate, methyl 4,4-dimethyl-3-oxopentanoate, ethyl bytyrylacetate, ethyl 2,4-dioxovalerate, methyl 3-oxo-6-octenoate, dimethyl 1,3-acetonedicarboxylate, diethyl 1,3-acetonedicarboxylate, di-t-butyl 1,3-acetonedicarboxylate, dimethyl 3-oxoadipate, diethyl 3-oxopimelate, dimethyl acetylsuccinate, diethyl acetylsuccinate, diethyl 2-acetylglutarate, methyl 2-cyclopentatecarboxylate, ethyl 2-cyclopentanecarboxylate, ethyl 4-methyl-2-cyclohexanone-1-carboxylate, ethyl 4-methyl-2-cyclohexanone-1-carboxylate, ethyl 3-(1-adamantyl)-3-oxopropionate, methyl 2-oxo-1-cycloheptanecarboxylate, N-t-butylacetoamide, 2-chloro-N,N-dimethylacetoacetamide, 4,4,4-trifluoro-1-phenyl-1,3-butanedione, 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione, 2-acetyl-1-tetralone, ethyl 2-benzylacetoacetonate, methyl 1-benzyl-4-oxo-3-piperidinecarboxylate hydrochloride, benzyl acetoacetate, acetoacetanilide, o-acetoacetotoluide, N-(2,4-dimethylphenyl)-3-oxobutyramide, o-acetoacetanisidide, 41-chloroacetoacetanilide, and 1,1,1-trifluoro-3-thianoylacetone.
When K is N in (V) and (XI), and R24 is nitrile, the ligand can made by the reaction of R22C(O)CH2CN with the diazonium salt of the corresponding arylamine, see for instance V. P. Kurbatov, et al., Russian Journal of Inorganic Chemistry, vol. 42, p. 898-902(1997). This paper also reviews methods of making ligands wherein K is CR27.
The boron containing ligands needed for compounds (VI) and (XII), 
can be made by known procedures, see for instance S. Trofimenko, Prog. Inorg. Chem., vol. 34, p. 115-210 (1986) and S. Trofimenko, Chem. Rev., vol. 93, p. 943-980 (1993).
The synthesis of the tropolone-type ligands required for (XVIII) and (XIX) are described in J. J. Drysdale, et al., J. Am. Chem. Soc., vol. 80, p. 3672-3675 (1958); W. R. Brasen, et al., vol. 83, p. 3125-3138 (1961); and G. M. Villacorta, et al., J. Am. Chem. Soc., vol. 110, p. 3175-3182 (1988). These can be reacted as described above to form the corresponding nickel complex.
The ligand for (XXVII) and (XXVIII), 
or either of its tautomers, 
can be made by reaction of the appropriate xcex1,"khgr"-dioxo compound such as a 1,3-dione or 1,3-dial or similar compound with the appropriate aromatic amine, see for instance J. E. Parks, et al., Inorg. Chem., vol. 7, p. 1408 (1968); R. H. Holm, Prog. Inorg. Chem., vol. 14, p. 241 (1971); and P. C. Healy, et al., Aust. J. Chem., vol. 32, p. 727 (1979).
If the ligand precursor may form a tautomer, the ligand itself may usually be considered a tautomer. For instance, the monoanionic ligand derived from (XXIX) and it tautomers may be written as 
In (XXVII) and (XXVIII) when L and/or G is N, the ligand can be made by the method described in Y. A. Ibrahim, et al., Tetrahedron, vol. 50, p. 11489-11498(1994) and references described therein.
The ligands for (XXXVII) and (XXXXI) can be made by methods described in Phosphorous, Sulfur and Silicon, vol. 47, p. 401 et seq. (1990), and analogous reactions.
The ligands for (XXXVIII) and (XXXXII) can be made by reacting R2PLi (from R2PH and n-BuLi) with propylene sulfide to form R2CH2CH(CH3)SLi, and analogous reactions.
The ligands for (XXXIX) and (XXXXIII), and for (XXXX) and (XXXXIV) are commercially available. Those used herein were bought from Aldrich Chemical Co., Inc., Milwaukee, Wis., U.S.A.
In the compounds (and ligands in those compounds) (I) through (XII), (XVIII), (XIX), (XXVII), (XXVIII), and (XXXVII)-(XXXXIV), certain groups are preferred. When present, they are:
R1 and R2 are both hydrogen; and/or
R3 is alkyl or aryl containing 1 to 20 carbon atoms, more preferably R3 is t-butyl; and/or
R1, R2 and R3 taken together are 
Ar1, Ar2, Ar3, Ar4, Ar5, Ar10 and Ar11 are each independently 
wherein R36, R37, R38, R39 and R40 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any 2 of R37, R37, R38, R39 and R40 that are vicinal to one another taken together may form a ring (for example the group 9-anthracenyl), and it is especially preferred that R36 and R39 are halo, phenyl or alkyl containing 1 to 6 carbon atoms, and it is more preferred that R36 and R3 are methyl, bromo, chloro, t-butyl, hydrogen, or isopropyl; and/or
R78 is Ar3, which is aryl or substituted aryl;
Ar1, Ar2, Ar3, Ar4, Ar5, Ar10 and Ar11 are each independently 2-pyridyl or substituted 2-pyridyl;
if a xcfx80-allyl group is 
then R4, R5, R6, and R8 are hydrogen; and/or
R4, R5, R6, R7, R8 and R9 are hydrogen; and/or
R4, R5, R6, and R7 are hydrogen and R8 and R9 are methyl;
one of R7 or R9 is xe2x80x94CO2R41 or chloro, and the other is hydrogen, and wherein R41 is hydrocarbyl, preferably alkyl containing 1 to 6 carbon atoms; and/or
R11, R12, R13 and R14 are each independently chloro, bromo, iodo, alkyl, alkoxy, hydrogen or nitro; and/or
R11 and R12 taken together form an aromatic carbocyclic 6-membered ring; and/or
R14 and R12 are both chloro, bromo, iodo, t-butyl or nitro; and/or
R11 and R13 are methoxy;
R14 is hydrogen and R12 is nitro; and/or
one or more of R11, R12, R13 and R14 are hydrogen; and/or
R16, R17, R18, R19, R20, and R21 are hydrogen; and/or
R16, R17, R18, R19, and R20 are hydrogen and R21 is methyl; and/or
K is CR27; and/or
R27 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group; and/or
R27 is alkyl, more preferably methyl; and/or
R24 is hydrogen, alkyl, cyano, or halo, more preferably hydrogen; and/or
R22 is hydrocarbyl or xe2x80x94OR117, wherein R117 is hydrocarbyl, more preferably alkyl containing 1 to 6 carbon atoms, or R22 is phenyl; and/or
R32 and R33 are both alkyl containing 1 to 6 carbon atoms or phenyl, more preferably isopropyl; and/or
R28 and R29 are both hydrogen or phenyl; and/or
R30, R31, R34 and R35 are all hydrogen; and/or
R31 and R32 taken together and R33 and R34 taken together are both a 6-membered aromatic carbocyclic ring having a t-butyl group vicinal to the R32 and R33 positions; and/or
R50, R51, R52, R53 and R54 are hydrogen; and/or
L is CR55 wherein R55 is hydrocarbyl, hydrogen, or substituted hydrocarbyl; and/or
G is CR57 wherein R57 is hydrocarbyl, hydrogen or substituted hydrocarbyl; and/or
more preferably R55 and R57 are both alkyl or fluorinated alkyl, more preferably methyl; and/or
R56 is hydrogen; and/or
Ar12 and Ar13 are both 2,6-diisopropylphenyl; and/or
R79, R80, R81, R82, R83, R84, R85, R86, R87, R88 and R89 are each independently hydrogen or alkyl; and/or
R90, R91, R92 and R93 are each independently hydrocarbyl, more preferably aryl, and especially referably phenyl; and/or
R94 and R95 are each independently hydrocarbyl; and/or
R96, R97, R98, and R99 are each independently hydrogen or hydrocarbyl; and/or
E is N or CR108; and/or
R108 is hydrogen or hydrocarbyl; and/or
R100, R101, R102, R103, R104, R105, R106, and R107 is each independently hydrogen, hydrocarbyl, or halo; and/or
R109, R110, R111, R112, R113, R114, R115, and R116 are each independently hydrogen or hydrocarbyl.
Specific preferred compounds (I)-(IV) and (VI) are given in Table A. The same groupings shown in the Table are preferred for the analogous compounds (VII)-(X) and (XII). In all of these compounds, where applicable, R4, R5, R6, R8, R9 [in (XX) above], R15, R16, R17, R18, R19, R20, R30, and R35 are all hydrogen (with the exceptions in the footnotes), R10 is hydrogen or methyl, R21 is hydrogen or methyl, and R7 is xe2x80x94CO2CH3 (with the exceptions in the footnotes). In compounds wherein L1 and L2 appear, and especially in compounds of formula (VIII) it is preferred that L2 is a nitrile, such as benzonitrile, p-methylbenzonitrile methyl nitrile, or pyridine or a substituted pyridine such as 2,6-dimethyl pyridine. A preferred L2 is an alkyl group, especially methyl. L1 and L2 taken together may be a xcfx80-allyl or xcfx80-benzyl group, but for all compounds in which L1 and L2 are present (i.e. combined) it is preferred that they are not a xcfx80-allyl or xcfx80-benzyl group.
Table B give specific preferred compounds for (V), (XXXVII) and (XXXIX) as well as the corresponding compounds (XI), (XXXXI) and (XXXXIII) respectively. In all of these compounds Ar5 is 2,6-diisopropylphenyl, K is CCH3, R24, R79, R80, R82, R85, R87, R88, and R89 are hydrogen, R90, R91, R92, and R93 are phenyl.
In a specific preferred compounds (XXVII) and the corresponding (XXVIII), Ar12 and Ar13 are 2,6-diisopropylphenyl, L and G are CCH3, and R56 is hydrogen.
In a specific preferred compound (XXXVIII) and the corresponding (XXXXVII), R94 and R95 are each cyclohexyl, R96, R97 and R98 are hydrogen, and R99 is methyl.
In a specific preferred compound (XXXX) and the corresponding (XXXXIV), R110, R111, R114 and R115 are hydrogen and R109, R112, R113 and R116 are methyl.
For clarity, the structures of compounds (Ia), (IIb) and (VIa) are shown below; 
In (XXXIII) it is preferred that:
R58, R59, R60, R62, R63 and R64 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group, and provided that any two of these groups vicinal to one another taken together may form a ring;
R66 is hydrogen, hydrocarbyl or substituted hydrocarbyl; and
R61 and R65 are each independently hydrocarbyl containing 2 or more carbon atoms, or substituted hydrocarbyl containing 2 or more carbon atoms.
R58, R59, R60, R62, R63 and R64 are each hydrogen; and/or
R66 is hydrogen; and/or
R61 and R65 are each independently alkyl, and more preferred that both are isopropyl or methyl.
In a preferred compound or ligand (XVIII) and (XIX):
R50, R51, R52, R53 and R54 are hydrogen; and/or
Ar10 and Ar11 are 2,6-dialkyl substituted phenyl, more preferably 2,6-dimethylphenyl or 2,6-diisopropylphenyl.
Monoanionic ligands which the olefins herein may add to include hydride, alkyl, substituted alkyl, aryl, substituted aryl, or R26C(xe2x95x90O)xe2x80x94 wherein R26 is hydrocarbyl or substituted hydrocarbyl, and groups xcfx80-allyl and xcfx80-benzyl groups such as xcex73-C8H13, see for instance J. P. Collman, et al., Principles and Applications of Organotransition Metal Chemistry, University Science Book, Mill Valley, Calif., 1987. Such groups are also described in World Patent Application WO 96/23010.
In compound (XXXVI) it is preferred that R68 is xe2x80x94OR117 or aryl, and/or R75 is hydrocarbyl or substituted hydrocarbyl, and/or R76 is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, more preferably hydrogen, hydrocarbyl or substituted hydrocarbyl.
In the second polymerization process described herein a nickel[II] complex such as any one of (VII)-(XII), (XIX), (XXVIII) or (XXXXI)-(XXXXIV) is either added to the polymerization process or formed in situ in the process. In fact, more than one such complex may be formed during the course of the process, for instance formation of an initial complex and then reaction of that complex to form a living ended polymer containing such a complex.
An example of such a complex which may be formed initially in situ is 
wherein R1 through R3, Ar1 and Ar2 are as defined above, T1 is hydride, alkyl, or R42C(xe2x95x90O)xe2x80x94 wherein R42 is hydrocarbyl or substituted hydrocarbyl or any other monoanionic ligand which ethylene may add to, and Y is a neutral ligand, or T1 and Y taken together are a bidentate monoanionic ligand which ethylene may add to. Similar complexes may also be formed with the ligands in (VIII)-(XII), (XIX), (XXVIII) and (XXXXI)-(XXXXIV). Such complexes may be added directly to the process or formed in situ.
After the olefin polymerization has started, the complex may be in forms such as 
wherein R1 through R31, Ar1 and Ar2 are as defined above, P is a divalent (poly)olefin group [the specific olefin shown in (XVI) and (XVII) is ethylene], xe2x80x94(CH2)xxe2x80x94 wherein x is an integer of 2 or more, and T1 is an end group, for example the groups listed for T1 above. (XVI) is a so-called agostic form complex. Similar complexes may also be formed with the ligands in (VIII)-(XII), (XI), (XXVIII) and (XXXXI)-(XXXXIV). Analogous compounds with other olefins in place of ethylene also may be formed. In all the polymerization processes herein, the temperature at which the olefin polymerization is carried out is about xe2x88x92100xc2x0 C. to about +200xc2x0 C., preferably about 0xc2x0 C. to about 150xc2x0 C., more preferably about 25xc2x0 C. to about 100xc2x0 C. The olefin concentration at which the polymerization is carried out is not critical, atmospheric pressure to about 275 MPa being a suitable range for ethylene and propylene.
The polymerization processes herein may be run in the presence of various liquids, particularly aprotic organic liquids. The catalyst system, olefin, and polyolefin may be soluble or insoluble in these liquids, but obviously these liquids should not prevent the polymerization from occurring. Suitable liquids include alkanes, cycloalkanes, selected halogenated hydrocarbons, and aromatic hydrocarbons. Hydrocarbons are the preferred solvent. Specific useful solvents include hexane, toluene, benzene, chloroform, methylene chloride, 1,2,4-trichorobenzene, p-xylene, and cyclohexane.
The catalysts herein may be xe2x80x9cheterogenizedxe2x80x9d by coating or otherwise attaching them to solid supports, such as silica or alumina. Where an active catalyst species is formed by reaction with a compound such as an alkylaluminum compound, a support on which the alkylaluminum compound is first coated or otherwise attached is contacted with the nickel compound precursor to form a catalyst system in which the active nickel catalyst is xe2x80x9cattachedxe2x80x9d to the solid support. These supported catalysts may be used in polymerizations in organic liquids, as described in the immediately preceding paragraph. They may also be used in so-called gas phase polymerizations in which the olefin(s) being polymerized are added to the polymerization as gases and no liquid supporting phase is present.
Included herein within the definitions of all the polymerization processes are mixtures of starting materials that lead to the formation in situ of the nickel compounds specified in all of the polymerization processes.
In the Examples all pressures are gauge pressures.
Quantitative 3C NMR data for the polymers was obtained using a 10 mm probe on typically 15-20% solutions of the polymer and 0.05M Cr(acetylacetonate)3 in 1,2,4-trichlorobenzene are 120-140xc2x0 C. For a full description of determination of branching by 13C and 1H NMR, and for a definition of branches, see World Patent Application 96/23010, which is hereby included by reference.